Oczhs



Patented Aug. 3, 1943 UNITED STATESPAZTENT OFFICE ANTHRAQUINONE cowoUNn James G. McNally and Joseph B. Dickey, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Jersey a corporation of New No Drawing. Application April 7, 1939,

V Serial No. 266,646

4 Claims. ((11. 260-279) This invention relates to the art of dyeing or coloring. More particularly, it relates to new anthraquinone dye compounds; 7

Organic derivatives of cellulose are characterized by an indifferent affinity for the usual cotton and wool dyes especially the ordinary water soluble dyes. Because'of this, it has been necessary.

cellulose formate, cellulose propionate or cellulose butyrate, and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose,

such as cellulose acetate-propionate, cellulose acetate-butyrate, and the cellulose ethers, such as methyl cellulose, ethyl cellulose or benzyl cellulose. 1 l l The anthraquinone dye compoundsof our invention are characterized in that they contain an group, wherein R and R1 each represents an amino group, an O-alkyl group, an O-ary1 group, an O-cycloalkyl group, an O-a1alkyl group or an O-heterocyclic group and R may be, in addition, an O-X group wherein X represents hydrogen, an alkali forming metal or a non-metallic substituent forming a basic salt, joined to a nitrogen atom which is a nuclear substituent of the anthraquinone nucleus through an aliphatic, cycloalkyl, or aryl radical. It will beunderstood,

of course, that O and P as used herein and in the I 1 claims, represent oxygen and phosphorus respec tively. f' g 1 'One or more acid ester of phosphorus groups of the character just defined may be present inthe anthraquinone dye compounds of our invention. However, as a general rule, no more than two such groups will be present. Again, ordinarily the acid ester of phosphorus group will be present an a-position of the anthraguinone dye nucleus although it may be in a fi-positiorn' "The anthraquinone dye compounds of our invention may contain monovalent substituentsin addition tothe herieinbeforeidefined acid ester of phosphorus groups. ,Where saidcompounds do,

contain one or more additional substituents'git may be a halogen atom such as chlorine or bromine, an alkoxy group such as ,methoxy',

ethoxy, propoxy, fl-methoxyethoxy e-ethoxyethoxy, or y-methoxypropoxy, a hydroxy group, an alkyl group such as methyl, ethyl, propyl, butyl, p-hydroxyethyl,p methoxyethyl, or [3- ethoxyethyl, an alkylamino group such as a nitro group, or an amino group, for example. It will be understood that the substituent groups just mentioned are intended to be illustrative and not limitative of theinvention. Ordinarily substituents, such as those just referred to, will be present'in an lat-position of the anthraquinone nu- Y cleus.

We are aware that anthraquinone dye compounds prepared by causing halides of acids of phosphorus to react upon aminoanthraquinones,

which have in at least one amino group at least one substituent containing a hydroxyl group, are known. Compounds of this type are described in British Patent No. 455,092. Examples given therein of aminoanthraquinones which have in at least one amino group at least one substituent containing a hydroyl. group are l-A-hydrOxybutylaminoanthraquinone,' 1 c oxy -chloropropylaminoanthraquinone, 1,4 di-(B-hydroXY- ethylamino) anthraquinone and anilidoanthraquinones which contain hydroxyl groups in the aromatic residue. whatsoever to such dye compounds.

The dye compounds of the prior art, just referred to, appear to be characterized in that they contain an oRz group, wherein R2 represents hydrogen or an alkali metal such as sodium or potassium. The dye compounds of the present invention difier structurally from the prior art compoundsjust mentioned in that only one of the B28 (in the groups characterizing the prior art compounds) can represent hydrogen or an alkali metal. In the compounds of the present invention, the second R2 must represent an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, or.a heterocyclic group. Further, in the compounds of the present invention, one or both of the OR2 groupings may be replaced by an amino group.

, willv be seenthat thecompounds of the present invention differ both. structurallyiand physically from the'compounds of the prior art and infact are new and distinct. compounds. I

The compounds of our invention containing an -oP o group wherein R and R1 have the meaning pre viously assigned tothem can'be prepared by reacting an aminoanthraquinone which has in at least one ainino group at least one substituent containing a hydro-xvi group joined to a carbon atom with a compound having the general formula: i

X.P=O

, wherein Arepresen'ts a halogen atom and B:and

X each-represents an amino group,'an O-alk'yl, an -0-aryl group, an (D-cycl'oalkyhgroup, 'an

' ,O-aralkyl group or an O-heterocyclic'group and B, inaddition, maybe ahalogenatom. When B isahalogen atom, the product initially .forrned is suh'jected'to hydrolysis'to form the desired product.--

The compounds of. our invention containing an Applicants make no claimgroup, wherein R and R1 have the meaning previously assigned to them, can be prepared by reacting an aminoanthraquinone which has in at least one amino group at least one substituent containing a hydroxyl group joined to a carbon atom with a compound having the general formula:

wherein A, B and X havethe meaning just assignedto'them; When B is a halogen atom, the product initially formed is subjected to hydrolysis to form the desired product.

Compounds having the formula:

/A XP=O wherein B represents a halogen atom and A and K have the meaning previously assigned to them maybe prepared by reacting a phosphorus oxyhalide with a compound having the formula ROI-L'wherein R represents an amino, an alkyl, an .aryl', a cycloalkyl,:an aralkyl, or a heterocyclic group. To illustrate, V

O=P.O C2115 1 Ol a can be prepared by reaction between phosphorus oxychloride, 'P0Cl3,-and.ethy1 alcohol. This compound can, in turn,.be reacted with an amino anthraquinone such as a-mono-fi-hydroxyethyl amino-anthraquinone, a compound which ha in at least one amino group at least one substituent containing a hydroxyl group joined to a carbon atom. Thereaction canibe illustrated as follows:

p H o N-CHaCH2-O'P=O ytk \CI I O o +Hol r n By hydrolysis with sodium hydroxide, for example,

a /H 0021-15 v t N-CHzGHr-OP=O o ll can be converted to H OCzHs Where B represents an amino group, an o-alkyl group, an O-aryl group, an O-cycloalkyl group, an O-aralkyl group or an O-heterocyclic group, dye compounds within the scope of our invention are obtained directly Without hydrolysis. To illustrate, where B is an alkoxy group such as methoxy, and X ismethoxy, the reaction proceeds as follows; l i

By the substitution of a hydroxyaryl compound such as phenol or naphthol, a hydroxycycloalkyl compound such as cyclobutanol or cyclohexanol or a hydroxyaralkyl compound such as benzyl alcohol or phenyl ethyl alcohol for ethyl alcohol in the reaction with the phosphorus oxyhalide, POCla, described above compounds of the general formula:

wherein A and. B each represents halogen and X represents O-aryl, o-cycloalkyl or Oaralkyl (in this compound A and B are chlorine and X I is OCzH can be prepared by reaction between phosphorus trichloride and 'ethylalcohol. "This compound. can, in turn, be reacted with an aminoanthraquinone such as a-mono-p-hydroxyethylaminoanthraquinone to obtain which, upon hydrolysis with sodium hydroxide can be convertedto V czHt N-CHzOHz-O-P The exact method employed' for the preparation of the anthraquinone compounds of our invention is dependent on the compound to be prepared. 'Wherethe only substituent to be present is an acid ester of phosphorus group connected through an aliphatic, cycloalkyl, or aryl radical with a nitrogen atom which is a nuclear substituent of the anthraquinone nucleus the compound may be prepared by reacting a hy- ONa droxy .(aliphatic, cycloalkyl, or aryli-aminoanthraquinone with a phosphating agent. Where two different acid ester of phosphorus groups are to be present, an ,anthraquinone compound containing two hydroxy (aliphatic, cycloalkyl, or aryl) -amino groups is reacted, for example, with the two different phosphating agent in succession. It will be understood, of course, that the first reaction is continued only until one equivalent of the phosphating agent is used up.

Where the desired anthraquinone compound is to contain both an acid ester of phosph'orus group connected to the anthraquinone nucleus, as statedherein, I. and another substituent, an amine radical, for example, a leuco anthraquinone, such as leuco quinizarinmay be condensed with a hydroxy (aliphatic, cycloalkyl, or"aryl)- amine and another amine, such as ethylamine, following which the compound resulting is phosphated to obtain the compound desired.

" Substituents, other than amino substituents,

may be introduced in the anthraquinone nucleus by known methods for introducing said substituents. r

The reactions above referred to may be carried out in a diluent or solvent medium such as water, ethanol, butanol, benzene, pyridine, dioxane, chloroform or dimethylaniline. Where a condensation involving a leuco anthraquinone is involved, the resulting leuoo compound may be oxidized to the non-leuco form in anysuitable manner. Where pyridine, for example, is the diluent medium employed, the oxidation may be carried out with air. The oxidation may likewise be carried out employing a perborate oxidizing agent, such as sodium perborate, for exam ple. This latter oxidizing agent is of general utility and may be employed in the case of all the diluent mediums above mentioned.

As previously indicated, .the anthraquinone compounds of our invention possess general utility for the dyeing of organic derivatives of cellulose. However, it will be understood, that the compoundsemployedfor this purpose should not contain a sulfonic acid group attached to the nucleus. Again, While the application of our compounds will be more particularly described with reference to cellulose acetate silk, a material to which they are especially adapted, they are of 7 utility for the dyeing of organic derivatives of cellulose, such as those mentioned herein, for example. The compounds of our invention,

whether sulfonated or unsulfonated, likewisepossess application for the dyeing of wool and silk.

The colors yielded on cellulose acetate silk are indicated hereinafter. Generally similar colors are produced on the other organic derivatives ofcellulose as Well as wool and silk.

While our inventiomas more fully shown hereinafter, relates generally to anthraquinone col-.

oring compounds having an acid ester of phosphorus group'joined through an aliphatic, a cycloalkyl, or an aryl nucleus to the anthraquinone nucleus, it relates more particularly to compounds containing but one anthraquinone nucleus. Compounds containing but one anthraquinone nucleus and wherein the connecting linkage is an aliphatic radical, especially an alkylene radical containing at least two carbon atoms, are

generally advantageous for the dyeing of organic derivatives of cellulose.

The following examples illustrate the method of preparation of the anthraquinone compounds of our invention. .7 I

Example 1v heated-to. boiling and the compound prepared n as describedaboveisslowly added with stirring. Hydrogen chloride is evolved during the reaction and when its evolution ceases; the chloroform is distilled off and the residue is treated with ice and sodium carbonate. 7 formed purified bydissolving in warm water, filtering and precipitating by the addition of sodium chloride. The precipitated dye is recovered by filtration, and dried. It has the probable formula:

and dyes cellulose acetate silk blue from awater solution.

. By the substitution of an equivalent molecular weight of 1-p-hydroxethylamino-4-'y-hydroxypropylamino anthraquinone for the lA-di-B-hy- 'droxyethylamino anthraquinone, a. dye having the probable formula:

, is obtained. Cellulose acetate silk is likewise "dyed-blue from water solutions of this dye compound, In employing the compounds of this The dye compound and the following examples as dyes, they may be applied tothe material undergoing dyeing or coloration. from water solutions or suspensions which may contain sodium chloride.

Example 2 The precipitated dye compound may be recovered by filtration and dried. It hasthe probable formula:

and dyes cellulose acetate blue from an aqueous solution which may contain sodium chloride.

Example 3 7.6 grams of methyl cellosolve are slowly added with stirring to 16 grams of phosphorus oxychlcridein 50 cc. of chloroform. The reaction mixture may be warmed slightly to complete the reaction following which the product formed may be recovered by distilling off the chloroform.

38.7 grams of l-n-butylamino-4-p-hydroxycyclohexylamino anthraquinone are added to 600 cc. of chloroform heated to boiling and the compound prepared as described above is slowly added with stirring. Upon completion of the reaction, the reaction product is Worked up as described in Examples land 2.i The dye compound formed has the probableformula:

. n O I ll U o H H d -0 11" ONa 5/ \l and dyes cellulose acetate silk blue from a Water solution which may contain sodium chloride.

Example 4 formula:

are slowly added with stirring. The reaction product is worked up in the same manner as described in Examples 1 and 2. A dye compound is obtained in which the. {8;hydroxyethylan1ino group in the 4-position is replacedby the V O CgH H NC2H4OP=O ONa aqueous solution which may contain sodium chloride.

, thraquinone are heated in 509 40 grams of The reaction may likewise be carried out in chloform with or without the presence of a base. Upon working up the reaction product, a compound is obtained which has the probable O NCH o H' i o thraquinone of the example and treating as de' scribed in the example, dye compounds corresponding to that just described, but inwhich the benzylamino group is replaced by the cyclohexylamino or pyridine group; may be obtained. These compounds likewise dye cellulose acetate silk bluevfrom their water solutions. P

Example 24 grams of leuco quiniz arin are dissolved in 200 cc. of normal butyl alcohol and reacted with 3.2 grams of methylamine. the reaction, 25 grams of ONa grouping. The dye compound obtained dyes cell lulose acetate silk a bluish green shade from an group in the 4-position. This dye compound colors cellulose acetatesilka blue shade from its water solution.

- Example 7 37.3 grams of 1,5-diethy lamino-4-bromoancc, of pyridine with '5- r l O and one gram of copper oxide. Upon completion of the reaction, all or nearly all of the pyridine is distilled off and the residue is poured into water. The desired dye compound may be precipitated by the addition of sodium chloride, filtered, washed and dried; It has the probable formula:

are added and the reaction mixture is heated until reaction is complete. The leuco dye formed is poured into water and oxidized in the usual manner with sodium perborate after which the dye is precipitated by the addition. of sodium chloride, filtered, washed and dried. An anthraquinone dye compound is obtained in which there is a methylamino "group in the l'-posit ion and a and dyes cellulose acetate silk bluish green shade from its aqueous solution.

I Example 8 24 grams of leuco quinizarin, 200 grams of normal butyl alcohol, and 50 grams of are refluxed together for about six hours. The reaction mixture resulting is poured into water and oxidized in the usual manner with an alkaline perborate such as sodium perborate. The dye compound formed can'be recovered by salting out with sodium chloride, filtering, washing and drying. An anthraquinone dye compound containing a group having the probable formula:

H OCH;

ineach of the 1 and 4-position s is obtained. This dye compound colors cellulose acetate silk deep blue shadesirom a water suspension.

The dye compound of this example may, likewise, be prepared by treating quinizarin with the amine given in the example in water on a steam bath. i

36 grams of are added to 600m. or chloroform and reacted with one molecular equivalent weight of I 01 0-0133 oi 1 :The dye compound formed may be recoveredby workingup the reaction mixture in the usual manner. A dye compound is obtained in which the -CH2OH group attached to the phenyl nucleus in the l-position of the anthraquinone nucleus is converted to the OCHa -CH2OP=O grouping. This dye I compound dyes cellulose acetate silk 9. blue shade.

Example 10 1 mole of 1-ethylamino-4-fi=hydroxyethylamino anthraquinone is placed in chloroform containing pyridine and reacted with 1 inole of O=P O among-o CH3 o1 or r I The reaction product resulting'is reacted with ethanolaifiine to obtain a compound wherein the B-hydroxyethylamino group originally present in I the 4-position is converted to a group; The dye compound colors cellulose a'cetate silk a blue'shade from an aqueous suspension. Ebiample 11 37.2 grams of l-methy lamino--fi-hydroxy- 'ethylamino anth'r'a'quinone are dissolved in dry pyridine and treated with 14.5 gram'sof i I OOH:

o=rol OOHz ppgn completion or the reauon; the reaction mixture is allowed to stand for some time after which it is poured into water, The dye compound formed may be recovered by .filtration,

washed with water and dried. By the above treatment, a dye compound isobtained in which the )6-hy-droxyethylamino group originally present in the 4-position is converted to a 7 H' .7 N-C2H4OP=O OCH:

group. This dye compound colors cellulose 'acetate silk a blue shade from an aqueous suspension; a

Example 12 29.2 grams of N-B hydroxyethylanthrapyrimidone are dissolved in pyridine and treated in the cold with and the reactionliscompleted by warming. Aqueous sodium carbonate is then added and the pyridine is removed by'ste'am distillation. The dye compound romeo ifiifici'liiteitd by the addition of sodium chloride, recovered by filtration, washed and dried. The dy'compound obtained has the ONa 0 II 0 V I and dyes cellulose acetate silk froth an aqueous solution. 7

l Emmplels 43.7 grams of the anthrapyridone having the formula:

a yellow shade are dissolved in dimethylaniline and treated in the cold with 16- grams of C [I C'2H'l=D-C&Hi0H and dyes 'celluloseacetate a v'i'olet red shade from an aqueous solution.

Example 14 -.-i g-ra-m mole of the ant hraquinone dye having the formula:- Y

is treated in dimethylcyclohexylamine with .1 gram mole of r o1 eer e-elm a as described in Example 12. The dye compound is worked up in the usual manner. By the above treatment, a dye compound is obtained in which the e-hydroxyethylamino group originally pres ent is converted to the group which, in its calcium salt form, has most probably. the formula: ...l= i

E l NU2Hl O --P=O oca z j dye compound dyes cellulose acetate silk a blue shade.

Example 32 grams of the pyrazoleanthrone having'the The reaction may be conducted as described in Example 12 and the reaction product may be worked up as described in said example. A dye compound is obtained in which the 'y-hydroxypropyl group originally present is converted to a group which has the probable formula:

' /'ONa Amigoc 0H5;

ca. y The dye compound obtained dyes'cellulose acetate silk a; yellow shade. v i a Example 16 23.5 grams or e-hydroxyethylaminobenaanf throne are treated in pyridine with one'equiva lentof i o1.. 0=P-O c115 The reaction may be carried out as described Example 12 and the reaction product may also be worked up'as described in said example. The dye compoundobtained has the probable formula: q

and dyes cellulose acetate silk a red shade.

Example 17 An anthraquinone acridone dye 'having' the formula: v

w H O p N l] O N-CHa istreated in the cold with POCls in pyridine and the reaction is completed by warming. The com pound resulting is treated with ammonia and the dye compound formed is worked up in the usual manner. A dye compound is obtained in which the hydroXyl group attached to the pheny nucleus is converted to a /NH2 -0-'P=0 NH2 group. This dye compound dyes cellulose acetate silk a blue shade.

Example 18 28.3 grams of 1-,6-hydroxyethylaminoanthraquinone are dissolved in 300 cc. of pyridine heated to C. and 22 grams of monoamyloxyphosphor'us dichloride in 200 cc. of pyridine are added dropwise with stirring While maintaining the temperature at 70C. Stirring and heating are continued'for seven hours following which the reaction mixture is poured into 200 cc. of water containing 16 grams of sodium carbonate. The mixture is concentrated to about one-fourth its volume under reduced pressure and upon cooling the desired dye compound crystallizes following which it is recovered by filtration, washed with water and dried. By the above treatment, a dye containing the I OCHzCHzCHaCHzCHa NG2H4OI I V ONa V grouping instead of the original e-hydroxyethylamino group is obtained. This dye compound colors cellulose acetate silk, wool, and silk purple shades. i

' Example 19 grouping is obtained. This dye compound colors cellulose acetate silk a blue shade from an aqueous suspension.

Example 20 37 grams of 1-p-hydroxyethylaminoL -hydroxypropylamino 5,8 dihydroxyanthraquinone are dissolved in 400 cc. of pyridine and reacted as in Example 18 with 30 grams ofmethoxyethoxys phosphorus chloride. The dye compound is worked up in the usual manner and contains a V I i OO2H5 w H -NC2H4OP OCH:

group in the 1-position and a OC2H5 H 'Nc3H -P group in the 4-position in place of the n-hydroxy-' ethylamino and -hydroxypropylamino groups originally. present in these positions. This dye compound colors cellulose acetate silk a 'gie'enishblue shade from an aqueous suspension. 1

' Example 21 '37 grams of 1,4,5 tri c-hydroxy'ethylamino an thraquinone are dissolved inpyridine and reacted with 25 grams of Example 22 31 grams of leuco-'1-,8-hydroxyethylamino-4- phenylaminoanthraquinone are dissolved in'a 'half and half mixture of dioxane and pyridine and treated at 70 C. with 20 grams of in accordance with the method described in Ex ample 18. The leuco dye compound formed is oxidized by passing in air and the reaction mixture worked up as'described in Example 18. A dye compound is obtained in which the s-hydroxyethylamino group present in the l-position is converted into a group havingthe probable formula:

This dye compound'colors cellulose acetate silk a blue shade.

' Example 23 V H .1 gram mole of leuco quinizarin, .l gram mole of p-fl-hydroxyphenetidine and 100 cc. of butanol are heated under reflux for six hours. The resulting leuco dye is then poured into-Water and oxidized with alkaline sodium perborate. The dye compound formedis recovered from themixture, dried and placed in- 500 cc. of dry chloro formfollowing which it treated'with'l gram mole'o'i a o=P-ocH3 The reaction mixture is warmed to complete the reaction. Chloroform is removed by distillation and the residue remaining is treated with aqueous sodium bicarbonate, dissolved in hot water and filtered. The dye compound formed is precipitated by the addition of sodium chloride, recovered by filtration and dried. By the above treatment, an anthraquinone dye containing a H /ONa -N-O-oon1l0-P o OCHa group in the 1-position and a hydroxy group in the 4-position is obtained. This dye compound dyes cellulose acetate silk a purple shade.

Example 24 .1 gram mole of a leuco 'anthraquinone containing a c I CHZ CHZ HCOC2H4OH GHQ-ca,

group in an a-position is treated with a phosphating agent such as The leuco dye compound resulting is oxidized and worked up in the usual manner to, obtain a non-leuco anthraquinonecompound containing a group in an a-position. Dye compounds of this general structure ordinarily yield blue shades on cellulose acetatesilk. By subjecting anthraquinone compounds containing a 13-hydroxy-,8-ethoxyethylamino group or a ,8"-hydroxy-p -eth0xy-,B-ethoxyethylamino group in an u-position to treatment with the phosphating agents of our invention, acid ester of phosphorus'groups may be substituted for the hydrogen atom of said hydroxy groups.

The dye compounds of our invention include anthraquinone compounds containing a group, wherein Y and Y each represents an aliphatic, cycloalkyL'or aryl residue, n represents a small whole number above 0 such as 1, 2, 3, or 4, and R and R1 have the meaning previously assigned to them, attached to the anthraquinone nucleus. Ordinarily Y and Y represent an 'alkylene radical such as ethylene. However, they can be, for example, the residue of a cyclohexyl or phenyl nucleus. 7 The preparation of anthraquinone compounds containing the specific groups designated above is more particularly indicated in Examples 23 and 24. Their method of preparation is believed to be clear from; the foregoing zero, such as 1, 2,; 3, or 4 and Z represents an description. i alkyl, an arylor a furylradical. The preparae In further illustration of compounds containtion of compounds of this typeQis illustrated in ing the above groups may be mentioned the examples which follow.

OCHa

omnngoznlon anthraquinone,

addition to an acid ester of phosphorus group,

i v r, H l p 'f In T 1n the scope of our invention and contain ng, in L9 gram-Sui of 1? pgjhydroxyethylammomonm benzoate-- -h drox eth lamin h i V an organic acid ester group, Constltute Very y an? raqul'nope valuable Series of dyes. While t e compounds are added 170739 0?. ofpyr dme and relate broadly to any organic acid ester group, 7 they relate more particularly toorganic acidester Q m: roups having the formula: 70 i ci I V w in cc. of pyridine are added with stirring. The Q f. reaction-mixture is heated at C. for seven 0' I a 3 hours and allowed to stand overnight following which it is pouredinto cc. of water containwhereinn representsasmall whole number above '15 mg 1 gram of sodium carbonate. The solution same resulting is filtered and evaporated to dryness under reduced pressure. The residue is then extracted several times with hot'ethanol'followin'g which the alcohol solutionobtained is filtered. The alcohol is removed whereupon a residue of dye weighing approximately 2.5 grams is obtained. The water soluble anthraquinone dye ob- I tained contains a group in the 1-position and a ONa --CH2CH2OP/ 0-heptyl group in the 4-position and colors cellulose acetate silk a blue shade. j i a Example 26 34 grams of 1,B-hydroxyethylamino-4-'y-hy- 'droxypropylamino anthraquinone are dissolved in 500 cc. of pyridine and treated with grams of o1 O=P0hcxyl in 200 cc. of pyridine. The reaction mixture is added to 70 C. for six hours following which 14 grams of caproyl chloride are added and the heating continued for one hour. The reaction product is worked up'as in Example 25. The anthraquinone dye compound obtained contains a H V NCzHiO(I 'lJ-C5 n group in the l-position and-a ONa H -N C aHuO P=O V O-hexyl group in the 4-position. This dye colors cellulose acetate silk, wool, and silk blue shades. I

Example 27 .1 gram mole of the anthraquirio'ne compound containing a phenylamino group in the l position, a p-hydroxyethoxy group in the 2-position removed under reduced pressure and the dye compound-formed allowed-to crystallize. By the above treatment,- the' B-hydroxyethoxy g een in I the 2-position is converted to the tetrah'ydro furoate form. The dye compound formed colors cellulose acetate silk, and silk blue shades.

Example 28 1 gram mole of theanthraquinonecompound containing cyci neryiamindgrdnp in the i-pegroup in the 2-position, a methylamino group in the 4-position, and a group in the 5 -p0sition is dissolved in pyridine and treated With 1 gram mole of methoxyacetic anhydride in accordance with themethod described in Example-27. .An anthraquinone dye is obtained in which the group in the 2-position has been converted into its methoxyacetic acid ester form. This dye compound colors cellulose i acetate si1k-,.woo1, and silk greem'sh blue shades.

Example 29 1 grain mole of the anthraquinone compound containing a I ,OOH:

H NC2H4OP\ '5 group in the 1-position and a ,B-hydroxyethylamino, group in the d position is dissolved in a pyridine-water mixture and treated with propioni'c anhydride in accordance with the method described in Example 25, for example.

By this treatment, the ,B-hydroxyethylamino group in the ii-position is changed into its propionic acid ester form. The dye compound obtained colors cellulose acetate, Wool, and silk bluish-green shades.

Example 30 34.7 grams of CH3 1- H N-C2H4-N-C2H4OH are heated with 140 grams of )4-methylamlno anthraquinone at 70 d. untntne evolution or hydrogen chloride teases. Most of the acid chloride is then removed under reduced pressure and the residue is treated with a cold dilute aqueous sodium bicarbonate solution. a The dye compound formed is recovered by filtration, washed with water and dried. By the above treatment, an anthraquinone dye is obtained in which the group originally present in the 1-position is converted to a OCHa group. This dye colors cellulose acetate silk a blue shade.

- Example 31 32.6 grams of 1,4-di-,8-hydroxyethylamino antnraeeinene are heat-ed'at "-7Q C. Withl-GG grams until the evolution of hydrogench-lori'de'ceases. Excess acid chloride isremoved under reduced pressure and the residue resulting is treated with dilute sodium hydroxide, warmed with Water and filtered while hot. The dye compound formed is precipitated from the filtrate by the addition of sodium chloride, recovered by filtration, Washed with water and dried. By the above treatment, an anthraquinone dye is obtained containinga .ONa

group in each of the land 4 positions. T This dye colors cellulose acetate silk ablue shade. f

Example 32 g 3.3 grams of 1,4-di--hydroxyethylamino "anthraquinone are dissolved in 50 cc. of pyridine and 2.25 grams of monoamyl phosphorylchloride dissolved in cc. of pyridine are slowly added with stirring. The reaction mixture resulting is heated one. water bath at 70 C. for seven hoursafter which itis left to stand overnight at room temperature. a The mixture resulting is poured into 200 cc. of a dilute sodium carbonate solution to efiect hydrolysis and this solution is evaporated to J dryness under reduced pressure. The residue remaining a'fter the evaporation is extracted-with ethyl alcohol following which the alcohol solution is filtered. The residue remainme after evaporation of the alcohol extract and a which constitutes theldesired dye product weighs 4.3 grams. The dye compound obtained contains a n l H I N o2H40-P=o= M ONa' groupgin the, l-position and a fl-hydroxyethyl amino groupin the 4-position and colors cellulose acetate silk a blue shade. Y

By reaction of 3.3 grams of lA- dio-hydroxyethylamino anthraquinone with 2 grams of butyl phosphoric acid dichloride in accordance with the procedure described above, a yield of 4 grams of f -oornc:moment) 1 ONa V 4-B-hydroxyethylamino anthraquinone can be obtained. This dye compound colors cellulose acetatesilk a blue shade.

Similarly, by reaction of 3.5 grams of ethyl phosphoric acid dichloride with 3.3 grams of 1,4-

di-fl-hydroxyethylamino anthraquinone in "ac- It will be understood that the foregoing exam-- ples are intended to be illustrative and not limitative of the compounds or our invention; Compounds containing a substituted. Representative of suitable substituents may be mentioned ahalogen atom; such as chlorine, bromine or iodine; an alkyl group, a nitro group and a hydroxy group. Suitable connecting linkages for joining the acid ester of phosphorus group to the nuclear nitrogen atom, in addition to those previously shown, in-

clude,'for example, butylene and the residue of cyclobutyl." i r Again, while those compounds obtained inthe form of a 'salt have been shown, for the 'most art, in their sodium salt form it will be understood that they can be prepared in the form of the salts previously set forth; They may, for example, be in the. form of their potassium, ammonium, calcium, ethanolamine or pyridine salt. Since the method of preparation of theseva-rious salts is believed to be clear to those skilled'in the art to which our. invention is directed, no ;de tailed description of' their preparation has been given. 1' x The anthraquinone dye compounds of our invention are, forthe. mostpart, soluble in water and may be applied to the materialundergoing dyeing from an aqueous solution of the dye. Those compounds which are insoluble or surficientlyinsolublein water,--as to render the use of a dispersing or solubilizing agent advantageous, may be employed for the direct dyeing of textile materialsby grinding the dye to a fine powder, intimately mixing it with a suitable dispersingor solubilizingwagent and adding the resultng mixture to water or a dilute solution of soap in water to form an aqueous dyebath. Following; this known preparation of the dyebath, the textile material or materials to be dyed may beadded to the dyebath and the dyeing operation conducted in known fashion. If desired, common salt may be added to promote exhaustion of the dyebath.

Dyeing operations can be conducted advantageously. at a temperature of -85" C. but any suitable temperature may :be employed. In accordance with the usual. dyeing practice, the material to be dyed will ordinarily be addedto the dyebath at a temperature lower than that at which the mainlportion of the dyeing is to be effected, a temperature, approximating 45-55 C., for example, following which the temperature of the dyebath will be raised to that, selected for carrying outthedyeing operation. The temperature at which the dyeing is conducted will vary somewhat depending on the particular material or materials undergoing coloration. It willbe understood that the anthraquinone dye compounds of our invention may be applied to the material to be colored in any "suitablemanner. Coloration of cellulose, wool and silk.

represented, for

may be effected, for example, by dyeing, print ing, or stencilling. Dispersing or solubilizing agents that can ,be employed for preparing suspensions of the insoluble or relatively insoluble dye compounds include soap, sulphoricinoleic acid, a salt of sulphoricinoleic acid, and sulfo' nated oleic, stearic, or palmitic acid or salts thereof, such, for instancaas the sodium or ammonium salts.

The following example illustrates how dyeing may be carried out-in accordance with our invention. Quantities are expressed in parts by weight. I

Example A -2.5 partsof the dye compound of Example 2 are added to 834 parts of water heated to 45-55 C. and lilo 'parts of cellulose acetate in the form of threads, fibers orfabric, for example, are enteredgand thetemperature raised to- 80185 C. The celluloseacetateisworked at this-temperature until dyeing, is: complete. The cellulose acetate is dyed a blue shade; If desired, spdium chloride can be added to aid in controlling the depth of dyeing and to promote exhaustionof the dyebath. .;.-:;7 r 7 Where aninsoluble or relativelyinsoluble dye compound of our invention is employed as the dye,-it will, as previously :noted, he first subjected to a dispersing or solubilizing treatment following which thedyeing 'operationmay be carried out in accordance withethe general method described above. 1

, While our invention has been illustrated inconnection with the dyeing 10f. celluloseacetate silk, it will 'beunderstood that dyeingoperations can be carried out in a manner similar tothat described abovexby the substitution of another organic derivative of cellulose material'or wool or silk for cellulose acetatesilk or by employing a dye compound other than that employed in the example or by'substitution of both the material being dyed and the dye compound of theexample.

We have further discovered that anthraquinone coloring compoundscontaining a thiophos- 5 phoric acid ester group-joined :to a nitrogen atom which is a nuclear substituent'of the anthraquinone-nucleus through an aliphatic, cycloalkyl, or aryl radical, similarly to'the acid ester of phosphorus compounds previously described, are likewise of utility for the dyeing of organic derivatives group can the most part, by the general Said thiophosphoric acid ester formula:

wherein R and .Rr each represents an amino group, an O-alkyl group, an 'O-laryl group, an O-cycloalkyl group, an O-aralkyl group, an O- 'heterocyclic group or ari O-'X-group,' wherein X represents hydrogen, an alkali forming metal or a non-metallic substituent' forming a basic salt.

' When theabove compounds are to be employed for the dyeing of an organic derivative of cellulose, such as cellulose imetate "silkv they should not contain a nuclear 'sulfonic acid group and preferably no 'carboxyiic vacid group-shouJd .be present in the anthraquinone nucleus. Further, compounds of the character, above described wherein R and R1 both represent an O-X group have not been found to be of much utilityjor the dyeing of. org-ani-c derivatives'of cellulose.v ,The

anthraquinone compounds described, whether sulfonated or unsulfonated, appear to possess rather general applicability for the coloration of silk and Wool. Anthraquinone coloring compounds containing a thiophosphoric acid ester group can be prepared by reactlng an aminoanthraquinone which has in at least one amino group at least one substituent containing'a hydroxyl group joined to a carbon atom with a 'cempound having the generalformula: I T '1 A .Xf'

wherein A represetns a halogen atom and B and Xeach represents an amino group, an O-alkyl, 'an-,O-aryl group, an O-cycloa-lkyl group, an

O-araikyl group oran Q-heterocyclic group and B, in addition, may be ahalogen atom. When B is halogen atom, the,..product 'initiaily formed is subjected to hydrolysis to form the desired product. 7. Compounds having the formula:

, m I A f m l 0 which, upon hydrolysis with sodium hydroxide, for example, can be converted to Where B represents an amino group, an O-alkyl group, an O-aryl group, an O-cycloalkyl group, an O-aralkyl group or an O-heterocyclic group, the desired dye compounds are obtained directly without hydrolysis.

Suitable phosphati-ng agents which may be employed in addition to those included in the above general formulae are phosphorus sulfochloride, PSC13, phosphorussulfobrornide, PSBrz, and phosphorus pen-tasulfide, P285.

, r r 2,326,047 It should be herenotd that whileB', R, R1

and 2. have been described as representing,

amongother things, an amino group, they are not limited to an unsubstituted amino group,- and amino as used herein and in the claims (unless.

otherwise indicated) is intended toinclude substituted amino such as alkylamino, for example, as well. Thatthis is so is apparent from an examination'of the examples given. These show I substituted amino groups. I

In accordance with the above teachings phosphating compounds having the general formula:

r =P 'N wherein D represents hydrogen or an alkyl' group may be employed. These can be prepared by reacting, in equal molecular proportions, phosphorus oxychlorlde with a compound having the general formula:

, e 13 v wherein D represents hydrogen or an alkyl group. Phosphorus oxychloride can be reacted, for example, with ammonia, methylamine, ethylamine, dimethylamine and ethanolamine JJHzCHzQH respectively. The corresponding thiophosphoric compounds can be obtained by substituting phosphorus sulfochloride for phosphorus oxychloride.

The preparation of these anthraquinone thio-- phosphoric acid "ester-compounds, can be illus:

trated by reference to Examples 1, 2 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 23;24, 26, 28,

30, 31' and-32 since, if the double bonded oxygen atom connected to the'phosphor'us atom of the phosphating compound of each of these examples is'replacedby anatom of sulfur and the general procedure describedin the examples is followed, corresponding thiophosphoric acidester compounds can be obtained.

The preparation of these thiophosphoricacid ester anthraquinone compounds will be made still more clear by the following example:

Example 33 3.3 grams of 1,4-di-p-hydroxyethylaminoanthraquinone are dissolved in 50 cc. of pyridine Q and 2.5 grams of monoamyl thiophosphoryl chloride dissolved in 25 cc. of l pyridine are slowly. added while the reaction mixture is well agitated.-

converted to agroup havingthe following probare substituted forthe monoamyl; hiophosphoroe chloride of the above example, an anthraquinone dye is obtained in which one of the rp-hydroxyethylamlno groups originally present is converted to a group having theprobableformula:

002115 11 V N-C2H40 I?;S

1 OCzHs v A yield-of ,4 grams is obtained. this case, the

dyev does not crystallize upon evaporation of the solution; However, the dye can be obtained by extraction of the residuewith'ethyl alcohol filterT-J ing the ethyl alcoholextract and evaporating oif the'alcohol to obtain the dye.-; 1 h q (Q1 t From the foregoing, the methodof'preparation of the anthraquinone dyes containing a thlophosphoricacid ester grouplshould be readily apparexit and no further specific examples showing their preparation is deemed necessaryg'fThese dyes may be employed for dyeingin an exa ctly similar manner as described in connection with the acid ester orphosphorus dyes of our invention. Further, we have discovered that aminoanthraquinone compounds containing an acid ing given hereinbefor'e) joined to anoxygen atom which is a nuclear substituent of the anthraqui- 'none nucleus through anialipha'tic; cycloalkyl, or

aryl radical, possess utility for the dyeingof or- 7 garnic derivatives og cellulose, wooland; silk.

Generally speaking these compounds wherein the connectinglinkage is an aliphatic radical are r n ee v;

When these compounds are to be employed for the dyeing of organic derivatives'oficellulose, such as cellulos acetate silk, they should not contain a, nuclear sul-fon-ic aoid group and preferably no 'carboxylic acid group should be prefs'ent'in the anthraquinone nucleus;- Compounds of ation s: silk and wool.

The nuclear oxygen atom: may be presentin either, an alpha of beta position; As above indicateu an aminozgrou must-elso'he present.

one or more'amino groups may; hezpreserit. v 01-;

din i fly t e amino gronn up s r sentlfi an alpha; position; Said amino canbe substituted with an alliy'l, arallcyl, Cycle described hereinbefore can be employed; Sim

crawl-radian ?e mlile fewer-teem derstood that the connectmghnkages mor 'rmly ilarly the same acid ester of phosphorus groups or thiophosphoric acid ester groups may be prescut.

7 The anthraquinone compounds in question can be prepared by reacting an aminoanthraquinone 7 compound containing an O,- (aliphatic, cycloalkyl, aryl) group, wherein the aliphatic, cycloalkyl or a-rylnucleus is substituted with a hydroxy group, a compmmd have thegeneraMm-rnula v I l 5 r and wherein .23 and x have't-he meaning previously assigned to them. These react-ions can be car rled out in accordance with "the preeedure set rorthinthepreoeding examples. l f preparation of the particular cempeunas in question will be madest-lll more clear by' the following-example:

3; Em fi 'qlfle grains or .il methylahiino-eethyIan inQ ZQ Bhydroxyethoxyantbrequinone are treated in offdryltetrachloroethahe w1th 1' ;gram V possess rather gener l p lic b ty forth 0 9? ester of phosphorus group or a thiophosphoric acid ester group (these terms having the mean- The reaction" mixture is warmed. to -complete the reactionz- The dye compound can be be recovered in: knownifashicn and has the probable formula: V. V

, a I H O' N-OH3 I H l -o-o2H 4-or l-o It dyes cellulose acetate silk a violet blue shade. As illustrative of other anthraquinone dyes contain-i-ng the grouping in question may be men- The method of 'preparation of these anthraquinone dyes should bereadily apparent from the foregoing description and no further specific ex- 7 amples showing their preparation is believed necessary. They yield, forthe most part, blue shades on cellulose acetate silk. Dyeing may be conductedwith them in an exactly similar manher as previously described.

'JOOzHrOCHQ We claim: 7 wherein R represents a member selected from 1. Ananthroquinone compound having the genthe group consisting of hydrogen and. a watereral formula: soluble salt-forming group.

R 3.The anthraquinone dye compound which in H Z its sodium salt form has the-formula: N-alk o P-O V V oomcmcmcm 0 CR1 v H V i N---CHzOHz0-P0 1 0 V 0N8 1 p 7 p 10 0 N-alk 1 y \C V n I! wherein alk represents an alkylene radical, R 0 g-(hm represents a member selected from the group con- I sisting of hydrogen and awater-soluble salt formm anthraqumone dye compound Whlch m group and R1 represents an group It-S Salt fOI'mhaS formula: 2. An anthraquinone dye compound having the I 003111 general formula: a 6

OR H c 0Na 1 I-oH,cHr-o-P==o c O-a1ky1 o i v i) N'CHI \C v V 11 V g gqlkyl JAMES G. McNALLY.

JOSEPH B. DICKEY. 

